JPH02200618A - Dentifrice containing aminoalkyl silicon modified - Google Patents

Abstract

PURPOSE: To obtain a dentifrice containing a modified aminoalkylsilicone, free from the tooth-coloration problem even by the use of an antibacterial agent, having improved taste and exhibiting excellent anticariogenic action. CONSTITUTION: This dentifrice contains at least one unit of the unit expressed by the formula I [(a) is 0-2 : (n) is 1-5; R is a univalent group; R<1> is a bivalent hydrocarbon group; R<2> is CH2 -CH(OH)-R<3> (R<3> is H or a univalent hydrocarbon group); (b) is 0 or 1; (m) is 1 or 2] and further preferably at least one unit of the unit expressed by the formula II (R<4> and R<5> are each a univalent group; (a) and (c) are each 0-3 and a+c is 0-3) in a vehicle permissible for the application to the oral cavity. The aminoalkylsilicone is preferably amodimeticone compound and its amount in the dentifrice is 0.5-20wt.%, preferably 1-5wt.%. The dentifrice is further compounded with an antibacterial compound (0.1-1wt.%), a moistening agent, a surfactant, an abrasive, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention This invention relates to dentifrices containing modified aminoalkyl silicone compounds.

Despite recent remarkable improvements in toothpaste products, there is a demand for even more improved products. Since the development of anti-cavity agents, particularly fluorides, has reduced the incidence of caries, the problem of gingival disease and periodontitis is receiving increasing attention in the industry. It has been proposed to incorporate antibacterial agents into consumer products for the purpose of treating periodontitis, but there have been problems with such use. For example, the use of chlorhexidine, a known antibacterial agent, has caused problems with coloration.

That is, the teeth, tongue, and oral mucosa were colored yellow to dark brown by chlorohexidine. In addition, chlorhexidine has the disadvantage of having a very strong taste.

Coloring also occurred when using cationic antimicrobial agents other than hexidine, such as hexetidine, alexidine, and other quaternary ammonium compounds.

Accordingly, there is a need for improved dentifrice compositions that contain chlorhexidine or other antimicrobial agents but do not stain teeth and have improved taste. It also has an excellent anti-corrosion effect (
What is also desired is a dentifrice having anticavityelects).

Coloration, whether caused by chlorhexidine or not, is a troublesome problem. The accumulation of color on the tooth surface is a cosmetic problem. Coloring can be promoted by food ingredients such as coffee, tea and red wine, and by smoking.

Dental plaque is a common cause of dental caries, gingivitis and staining, and plays a major role in their progression. Current common oral hygiene practices dictate that plaque must be removed or prevented for cosmetic purposes and to eliminate potential pathologies of the teeth and gums.

Dental plaque begins to form as a result of caries bacteria adhering to the epithelium, the bacterial membrane on the tooth surface. These sticky bacteria alter and reproduce food components and accumulate to form a sticky deposit known as dental plaque. Dental plaque generally consists of bacteria and bacterial end products such as polyzaracalides, inorganic salts and salivary proteins. Plaque bacteria convert carbohydrates into m-acids, which deionize enamel and form cavities. Dental plaque acts as a nucleus for the formation of calculus (tartar), which is mineralized dental plaque with ligneous calcium phosphate salts. As the stone matures and hardens, significant coloration is observed due to absorption of food chromogens. Unsightly calculus deposits at the gum line cause gingivitis and periodontitis.

It has already been suggested to incorporate silicones into dentifrice compositions to coat the teeth with silicones and thereby prevent cavities and staining. For example, British Patent No. 689.6
No. 79 discloses a mouthwash containing organopolysiloquiline to prevent tar, stains, tartar, and food particles from adhering to the teeth, or to remove these substances from the teeth. . However, polymers such as those disclosed therein have not been very effective in protecting teeth. This is because it has been found that polysiloxane does not adhere to teeth for long periods of time. Therefore, there remains a need for dentifrice compositions containing hydrophobic materials that effectively coat teeth.

U.S. Patent No. 3,624,120 Specification 1 (Yette
r) discloses quaternary ammonium salts of cyclic siloxane polymers, which are cationic surfactants,
It is said to be effective as an antibacterial agent and an anti-corrosion agent. In the case of better, it is believed that the siloxane polymer absorbs onto the calcium phosphate to form a film that reduces the rate of acid dissolution. However, yetterO) cyclic, low molecular weight, high N/S i
It is not anticipated that the dissolution of the chemical compound could result in the formation of a highly hydrophobic film on the tooth surface. Also, Yet
From the description in ter, it is not recognized that the low molecular weight constant compound is useful for preventing coloring. Another problem with Yetter compounds is their high cost due to the high N/Si ratio. The toxicity of compounds with high N/Si ratios is also questionable.

A pending application filed concurrently with this application (Viccar O et al.
Name of the invention
ng Am1noalkySilicones”)
discloses dentifrice compositions containing aminoalkyl silicones to coat teeth and prevent staining and erosion. Aminoalkyl silicones were found to be more permanent than alkyl silicones due to the interaction of the positively charged nitrogen of the amine with the negative charges on the tooth surface.

However, ami/groups have a tendency to react with certain groups in dentifrice ingredients, such as aldehydes in fragrance ingredients. Therefore, there is a need for aminoalkyl silicones having amino/groups that have low reactivity but can be protonated over a wide pH range.

Attempts have also been made to modify (modify) the structure of aminosilicone in order to reduce the reactivity of the amine group. US Pat. No. 4,507,455! In this case, amino silicone and acetic anhydride are reacted to form an amide. This modification will result in the amine being protonated F)
It is believed that this greatly limits the 1-1 range, thereby impairing the usefulness of aminoalkyl silicones in applications where the 1]1 henylation of amines as described above is important.

In addition, US Pat. No. 4,472,566 discloses that amine silicone and benzyl chloride are reacted and
It is also disclosed that a tertiary amine is formed.

For US patents 3. (Moreh No. 132,577)
ose) discloses that organosiloxanes are useful for various applications in the field of synthetic polymers, particularly as NPI agents for aqueous dispersions of clays. The organosiloxane of the HOrehQuSe patent contains units of the formula:

(HOZ) 2-a NCoH2o(Rb)S i 0
(3-b) /2 In the above formula, 10Z- is a divalent group derived from t-noeboxide by opening the oxirane ring, and OH is bonded to N via two carbon atoms. , a is an integer of 0 to 1, n is an integer of 3 to 15, R is hydrogen, a monovalent hydrocarbon group, or C, H2n (R1)) SI 0 (3-b) /2 It is. There is no description in 5 orehousa suggesting that the compound is useful in dentifrices etc.
e does not seem to recognize any potential use of compounds that can produce higher positive charge densities.

SUMMARY OF THE INVENTION Applicant has disclosed that a dentifrice containing a novel compound selected from the group of aminoalkylsilyl compounds having formulas A and B and a compound selected from the group of compounds having formulas C and D prevents tooth staining. It was discovered that a hydrophobic barrier is formed on the tooth surface in order to prevent cavities. Additionally, the aminoalkyl silicones used in the present invention have been modified to retain positive charge over a wide pH range while reducing the reactivity of the amine groups toward aldehydes and other reactants. The antistaining properties of the dentifrices of the present invention are particularly pronounced when the compounds of the present invention are used in combination with antimicrobial agents such as clo['hexidine]. The use of aminoalkyl silicones in these cases can accelerate the problem of discoloration or react with fragrance components such as aldehydes, using antibacterial compounds to prevent bacterial and gingival diseases. It is possible to suppress stains and caries. The anti-color properties of the modified aminoalkyl silicones of the present invention are also useful when incorporating other coloring ingredients, such as tin fluoride, into dentifrices. In a preferred embodiment, the modified aminoal 4-yl silicone comprises amodimedine.

The modified silicones of this invention are prepared by treating silicones containing primary or secondary amine functionality with an epoxide, such as ethylene oxide. This reaction effectively converts many amines to tertiary amines having one or two β-hydroxyl hydrocarbyl substituents. Reaction of the primary amine forms a tertiary amine having two β-hydroxylhydrocarbyl tetrasubstituted groups. Due to the third molecular structure and the electron withdrawal properties of β-human[]xyl, the reactivity of riazine is reduced, but the pKa is maintained between 7 and 9. Therefore, these new silicones are cationic polymers and have good physical interaction with substrate surfaces, but poor chemical reactivity towards fragrances, colorants and skin.

In a preferred embodiment, the novel modified silicone contained in the dentifrice of the present invention consists of an organosyxane containing at least one unit having the formula:

R2111N-(C1''2CH2N). -RS i 0
(3-a) /2 Δ2bRa In the above formula, a is 0 to 2, n is 1 to 5, R is a monovalent group, and [(1 is a divalent hydrocarbon group) , R is -0H2-OH(OH)-R3, R3 is selected from the group consisting of hydrogen and a monovalent hydrocarbon group, b is O or 1, and m is 1 or 2.

R is preferably a hydrocarbon group, a halogenated hydrocarbon group,
selected from the group consisting of hydrogen, hydroxyl groups and alkoxyl groups. Particularly preferred are methyl, phenyl and trifluoropropyl. 1-10, especially 1-4
Groups containing 5 carbon atoms are preferred. The divalent hydrocarbon group for R1 preferably contains 1 to 20 carbon atoms, more preferably 3 to 20 carbon atoms.

Most preferred are hydrocarbon groups containing 3 to 5 carbon atoms. Preferred R3 groups include hydrogen, hydrocarbon groups, methyl, phenyl. When R3 is a hydrocarbon group,
The group preferably contains no more than 10 carbon atoms, more preferably no more than 4 carbon atoms. Particularly preferred are hydrogen and methyl. n is preferably 1. m is preferably 2. b is preferably 1.

Examples of units having formula A are shown below.

And preferably, units having the formula B are present in the aminoalkyl silicone together with units having the formula B below.

Ra Rc S 1O(4-a-c) 72
B In the above formula, R and R5 are the same or different monovalent groups, and a and C
is 0. 1. It is an integer of 2 or 3, and a+c is 0.
1. 2 or 3.

Preferably R and R5 are hydrocarbon groups, halogenated hydrocarbons, hydrogen, hydroxyl or alkoxyl. R and R5 usually contain 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 4 carbon atoms. Particularly preferred as R and R5 are methyl, fer and trifluoropropyl.

A+C is particularly preferably 2.

The modified amino silicone of the preferred embodiment of the invention has the formula A
and preferably a unit having the formula B in a random copolymer block copolymer,
Contains in the form of linear or branched polymers. The amount of goldstone in units having the formula 鈥擟 in the polymer is from 0.5 to 100% by weight, preferably from 1 to 10% by weight. The molecular weight of the polymer is preferably 5000 to ioo, ooo. Molecular weights above 5000 are particularly preferred as the compounds effectively form a hydrophobic barrier to the tooth surface.

The preferred upper limit of molecular weight is 100,000. 50~
A viscosity of 3000 cps is preferred.

Examples of preferred modified polysiloxanes in the present invention are as follows.

In the above formulas, x = 1005 y = 50 and 81 counterions In the case of units of preferred formulas A and B, the use of multiple nitrogens per side chain results in a maximum positive charge density resulting in aminoalcohols on the tooth. Dentifrices formulated with aminoalkyl silicones of formulas C and D may also be used effectively, although gil silicones are believed to be more suitable. Therefore, the present invention includes:
At least one unit of the formula C (wherein a R1, R2 and m are as defined above) and at least one unit of the formula % (wherein R, R, a and C are as defined above) ) Also included are dentifrices consisting of organosiloxanecobolin containing at least one unit having the following.

The modified aminoalkyl silicone of the second embodiment of the present invention comprises at least one unit having the formula C and at least one unit having the formula in a random copolymer, block copolymer, linear polymer or branched polymer. Contains in the form of The content of units with formula C in borine is 0.
5 to 100% by weight, preferably 1 to 10% by weight.

The molecular weight of borine is preferably 5000 to ioo, o
It is oo. Molecular weights above 5000 are particularly preferred as the compounds effectively form a hydrophobic barrier to the tooth surface.

The upper limit of the preferred molecular weight is 100.000. 50~
A viscosity of 3000 cps is preferred.

An example of a preferred modified aminoalkylsiloxane in the second embodiment of the present invention is a compound containing at least one unit having the following formula.

1-(OCH2C1-12 \ N-Cl-12Cl-12CH2-8+ 0/ HOCI-12CI-12CI-13, Detailed Description of the Invention The compounds of the present invention are prepared by mixing an epoxy compound and an amino silicone in a pressure reaction vessel. and heating for about 24 hours, after which unreacted 1-bogiside compound is removed in vacuo. The amount of epoxide to be used is calculated based on the number of amine functions on the aminoalkyl silicone. Preferably. converts the primary and tertiary amines into tertiary amines by reacting two epoxides with all primary amines and reacting one T-base with all tertiary amines.Stoichiometry An excess of epoxide of up to 25% can be used.The reaction is preferably carried out at 25-150°C, especially 50-100°C.The pressure is 50-300 psi.
In particular, it is preferable to maintain the pressure at 50 to 150 psi.

Although Applicants do not wish to be limited to any particular theory of operation of the present invention, it is clear that when the modified aminoalkyl silicone contacts the water of any I)l-1, the pendant It is believed that the nitrogen or end gapping nitrogen becomes protonated and the cations thus formed are attracted to the negatively charged phosphate ions on the tooth. Thus, the hydrophilically charged pendant 1 portion or end capping portion of the aminoalkyl silicone is attracted to the tooth, forming a hydrophobic alkyl silicone scaffold anchor that forms a film on the tooth and protects the tooth from staining and caries. do. the β-human 0-oxyhydrocarbyl group attached to the amine-nitrogen reduces the properties of the nitrogen and reacts with aldehyde groups and other reactive groups found in toothpaste;
At the same time, increasing the number of aminoalkyl groups per nitrogen molecule increases the persistence of silicon.
ity) will be improved.

The increased permanence of aminoalkyl-containing silicones allows them to provide enamel with a durable waterproof barrier that is compatible with cationic antimicrobial/antiplaque agents. Aminoalkyl silicones do not adversely affect the antiplaque activity of chlorhexidine. On the other hand, increasing the number of aminoalkyl groups per molecule improves the bonding of the molecule with the tooth surface and at the same time also increases the solubility of the polymer and reduces its hydrophobicity. Consequently, in all embodiments of the invention, it is preferred that the aminoalkyl groups constitute 1 to 60%, preferably 5 to 30%, of the repeat units of the polymer. In other words, the number of silicone atoms with nitrogen-containing moieties attached to the silicone atoms constitutes 5-30% of the total number of silicone atoms.

2/1 The toothpaste of the present invention can take several forms. For example, the toothpaste may be a toothpaste, cream or gel, or may include a mouthwash, or may be an oral spray or chewing gum. In a preferred embodiment thereof, the modified amine-functional silicone [amodimethicones] of the present invention
or other aminoalkyl silicones] are present in emulsified form. In a particularly preferred embodiment of the invention, antimicrobial compounds, such as chlorhexidine or quaternary ammonium salts, are included in the toothpaste together with the modified amine-functional silicone. Typical toothpaste ingredients include, of course, depending on the form of the toothpaste.
! obtain. Toothpaste creams and gels generally contain one or more abrasives and may also contain wetting agents, binders, surfactants, alcohol, flavoring agents, sweetening agents and water. Gargle solutions generally contain alcohol, humectants, surfactants, and flavoring agents.

It will contain sweetener and water. Toothpastes can also take the form of denture cleaners.

The main importance of the present invention in the topical setting of gingivitis is believed to be that it allows the use of chlorhexidine, quaternary ammonium compounds and other antimicrobial compounds during tooth brushing without staining the teeth; At the same time, the compositions of the invention may also be beneficial in preventing gingivitis by reducing or preventing dental plaque.

In fact, as mentioned above, dental plaque is a common factor in tooth decay, gingivitis, and staining, and contributes significantly to the development of each of these problems.

It is believed that the alkylamino silicone films □ of the present invention will prevent the adhesion of stains such as chlorhexidine while promoting the removal of such stains from the teeth. The toothpaste of the present invention is cosmetic insofar as it makes it possible to reduce staining! It would also serve the interests of the East. The compositions of the present invention also reduce the pain and progression of root cavities due to coating action, reduce unpleasant taste from dental product ingredients such as antimicrobials, surfactants, etc. and can prevent tartar growth.

A preferred class of aminoargyl silicones are amodimethicones.

The aminoalkyl silicone of the present invention is preferably acyclic. In order to sufficiently deposit the silicone on the teeth,
It is important that the silicone is not cyclized. There is no theoretical upper limit to the molecular weight of the silicone, as long as the silicone is spread over the tooth enamel by the brushing effect or by rinsing.

A compound with a molecular weight of 10.000 to 30.000 is
Lower molecular weight compounds would be expected to produce more durable films. High molecular weight Syrian] forms a more stable film on the enamel surface,
On the other hand, lower molecular weight silicones tend to disperse faster. High molecular weight and low molecular weight silicones can also be mixed together to obtain a mixture of the desired viscosity.

The toothpaste of the present invention preferably contains 0.5 to 20% by weight, more preferably 1 to 5% by weight of the modified organosiloxane polymer.
It consists of a mixture containing % by weight. In addition to the modified aminoargyl silicone, the toothpaste also contains 0,001 to 3% by weight, more preferably 0,001 to 3% by weight of an antibacterial compound, such as an antibacterial quaternary ammonium compound or chlorhexidine.
．． It may be contained in an amount of 1 to 1% by weight. A preferred antimicrobial compound is chlorhexidine. The modified aminoalkyl silicones of the invention may be used in the toothpastes of the invention in the presence or absence of antimicrobial compounds.

The modified aminoargyl silicone of the present invention can be incorporated into toothpaste as a silicone oil or as a silicone emulsion, preferably as an emulsion.

Nonionic surfactants and/or cationic surfactants are suitable emulsifiers.

Cationic quaternary ammonium surfactants such as tallow trimethylammonium chloride and cetylpyridinium chloride may be conveniently used, and in addition to being emulsifiers, these also have health benefits such as preventing plaque. Provides benefits (antibacterial agents).

The amines of the present invention are protonated and have a positive charge when 1u14 is below their pKa.

Depending on the structure, pKa ranges from about 7 to about 9.5. The FIH of the toothpaste of the present invention should be 9.5 or less, preferably 6 to 8, which protonates the aminoalkyl groups and prevents decomposition of the siloxane polymer.

Suitable toothpastes are toothpaste creams and gels and mouthwashes. Ingredients that may normally be contained in toothpastes and gels and that may be used in the toothpaste and gel compositions of the present invention include abrasives, foaming agents, flavoring agents, humectants, binders, sweeteners and water. be. Anti-calculus agents may be added to increase the anti-calculus effectiveness of the compositions of the present invention.

Abrasives that can be used in the toothpaste of the present invention include alumina and its hydrates such as α-alumina trihydrate, magnesium trisilicate, magnesium carbonate, aluminosilicates such as aluminum silicate and calcined silica. aluminum acid, calcium carbonate, zirconium silicate,
Examples include polymethyl methacrylate, powdered polyethylene, and silica. Depending on the form tooth brushing should take,
Especially in the case of toothpaste, the abrasive is 0 to 70% by weight,
Preferably 1 to 70% by weight, more preferably 10 to 10%
It may be present in an amount of % by weight.

Wetting agents contemplated for use in the present invention include glycerol, polyols, sorbitol, poly-1-ethylene glycol and propylene glycol. Humectants, especially in the case of toothpastes, are usually present in amounts of 0 to 80% by weight, preferably 5 to 70% by weight. Thickening agents suitable for use in the present invention include silica. Thickeners may be present in toothpaste creams and gels in amounts of 0.1 to 20% by weight.

Binders suitable for use in the toothpastes of the present invention include hydroxyethylcellulose (Natrasol) and hydroxyethylcellulose (klucel). It is preferred to avoid anionic binders since they are believed to form complexes with the supra-nium cations of protonated aminoalkyl silicones. Binders may be present in the toothpaste of the present invention in the range of 0.01-3%. Sweeteners suitable for use in the toothpastes of the present invention include saccharin, the preferred sur! 1 is about 0.1 to 5%.

A variety of pyrophosphate salts and other polyphosphate salts have been described in U.S. Pat.
, 515,772 and 4,627,977. These salts include di- and tetra-alkali metal pyrophosphates, where the alkali metal is preferably selected from the group consisting of sodium and potassium. Because phosphates tend to react with aminoalkyl silicones,
Although phosphates are generally not preferred, the inclusion of these anti-calculus agents may be appropriate in formulations of the present invention. Zinc salts are described in U.S. Pat. No. 4,100,269 and U.S. Pat.
No. 325 and No. 4,339,432 (along with glycine) as an anti-tartar agent. These may also be included in the composition of the invention.

A surfactant may be included as a foaming agent. Although sarcosinate surfactants are beneficial, as discussed above with respect to emulsifying silicones, it is preferred that the surfactants used in the toothpastes of the present invention be nonionic or cationic.

The surfactant is 0 to 15% by weight, preferably 0.1 to 15% by weight.
It may be present in weight percent, more preferably in the range 0.25 to 10 weight percent.

Flavoring agents can be present, for example, from 0.01 to about 5% by weight, especially from 0.1 to about 5% by weight.
It is usually included in toothpaste in small amounts, such as 5% candy. Any type of flavoring agent may be used, even flavoring agents having aldehyde groups. Low aldehydic and non-aldehydic flavoring agents are generally preferred. This is because amines in modified silicones are generally expected to react with the acyl groups of aldehydes to form Schiff bases that cause color and prevent the nitrogen atoms on the silicone from interacting with the tooth surface. . However, the aminoalkyl silicones of the present invention are modified to reduce the reactivity of the amine nitrogen. As a result, the level of aldehydic and other amine-reactive moieties is at a low impact level.

Fluoride sources used in toothpastes may also be included, a specific example of which is sodium fluoride.

Examples include tin fluoride, sodium monofluorophosphate, zinc ammonium fluoride, stannous ammonium fluoride, calcium fluoride, and cobalt ammonium fluoride. Fluoride ions typically range from O to 1500 pDi
, preferably at levels of 50 to 1500 ppm, but higher levels up to so-called 3000 ppm may also be used. Casein and its hydrolysates are other effective anti-caries agents and are used, for example, at levels of 0.1-5%.

Titanium dioxide is a suitable white dye.

The above ingredients suitable for toothpastes are also generally suitable for gels, as will be clear to those skilled in the art of toothpaste and gel formulations. Accordingly, references to toothpaste should be construed to apply equally to gels, except as noted.

Typically, mouthwashes consist of an aqueous/alcoholic solution, flavoring agents, humectants, sweetening agents, foaming agents and colorants. The corresponding compounds mentioned above for use in toothpastes are likewise normally applicable within the ranges mentioned above for gargling solutions. The mouthwash may contain ethanol at a level of 0-60% by weight, preferably 5-30% by weight.

Chlorhexidine or other antimicrobial agents, such as quaternary ammonium antimicrobial compounds, are included in the toothpastes of the present invention, but preferred concentrations thereof may range from 0.001 to 3%. Particularly preferred is a rollhexidine concentration of 0.1
It is in the range of ~1%.

Cetylpyridinium chloride, hexetidine, alexidine, phenolic resins [e.g. DP 300 exCiba
Ge1n and salicylamide (including salicylanilide)] and sources of metal ions such as zinc, copper, silver and tin (e.g. zinc chloride).

Copper chloride, tin chloride and silver nitrate) are also suitable antimicrobial agents. Coburn et al., US Pat.

Suitable dyes/colorants for toothpaste, such as FD&C Blue #
1. FD&C yellow #10. FD&C Red #40 and the like may also be used during tooth brushing of the present invention.

The aminoalkylborisiloxanes of the present invention may be endcapped, and if so, the one or more endcapping groups (Re) preferably contain one or more 11 to xylated nitrogen atoms.

As mentioned above, a preferred class of monoalkyl silicones, which react with evogicide to form the modified compounds used in the toothpaste of the present invention, are the amodimethicones. Amodimethicone is a polydimethylsiloxane polymer containing aminoalkyl groups. An aminoalkyl group is, for example, n-propylamine or n-propyl-
N-ethylenediamine may be present, and these groups may be present pendant or at one or more ends of the polydimethylsiloxane chain.

Amodimethicone is commercially available. Specific examples of commercially available amodimethicone include Dow CorninO's DC
-929, DC-02-7224 and Q2-8075. These polymers contain aminoalkyl groups attached to a primary polydimethylsiloxane structure. 02
A typical depiction of the aminoalkyl group-containing unit of 8075 is e O-8t -C,H2,N1-10H2C82NH,
.

It is.

As mentioned above, for example, the following unit: (HOCH2
C1-12> 2 NCH2CH2N-CH2CH2
Particularly preferred are ethoxylated and propoxylated amino silicone compounds containing multiple nitrogen groups per silicon atom (formula A above), such as compounds containing Cl-1, S + OH2CH3 CH2. The reason for this is that these compounds have a higher positive charge density than J: upon pronation. These compounds are fully described in Lin et al., U.S. Patent Application "Hydroxyl Hydrocarbyl Modified Aminoalkylsilynes" filed concurrently with this application, which is also incorporated herein by reference.

Unless specified or required by the text, percentages of ingredients are percentages by weight.

The invention will be further illustrated by the following specific examples, but the invention is not limited thereto.

Alkylation of Amine-Functional Silane Monomers Example 1 N-2-aminotin-del-3-aminopropyltrimethoxysilane [obtained from PetrarCh]
50g, propylene oxide (obtained from Aldrich)
39.2 g and 2-propatool 909 were reacted together and then the solvent was removed.

The product was a reactive silicone that precipitated out during the amine titration.

Alkylation of Amine-Functional Polydimethylsiloxane Copolymerization Example 2 In a cooled Parr pressure reactor, amodimedicone oil (a
80 tJ of modimethicone) (1) and 6.5 g of ethylene oxide were added. Then, the contents were reduced to 10
Heat at 0 psi, 50° C. and stir for approximately 24 hours.

An exotherm to 75°C was observed within 0.5 hours of the start of the reaction. After 24 hours of reaction, heating was stopped and the contents were cooled to room temperature. Thereafter, the pressure in the reactor was returned to normal pressure by slowly bubbling through a sodium hydroxide solution, and unreacted epoxide was removed. Then, the remaining epoxide was distilled off under reduced pressure.

The amine content (total, 2nd - 3rd and 3rd) of the product was determined by potentiometric titration [OHicial and tentative method].
e methods of the Amer
ican Oil Chemists 5oIiety
) See Tf 1a-64 and Tf2a-64>.

' - t'L' result - Example 2: Total amine @ (1° + 2° to 3°): 1000
10-6 mol/g tertiary amine presentation (3°):
929X 10-''mol/g This result shows that 93% of the total amines are present in the form of tertiary amines.

Example 3 Same as Example 2, amodimethine oil (1) 2!
i0g and 33g of propylene oxide were initially
C. and 100 psi until an exotherm of about 70.degree. C. was observed. After exotherm, the reaction was carried out at 100° C. and 100 psi for about 20-24 hours. As in Example 2, unreacted epoxide was removed and the product was analyzed.

Titration results Example 3: Total amine amount: 1110x 10'mol/g
23rd amine constant: 1077x 10'n+ol/
sj tertiary amine amount: 947x 10-”1T
Approximately 85% of the total amine amount in lol/g was converted to the tertiary amine form.

Husband 1'' [(± 5opropanol H2) Similarly to Example 2, (1) 759 and cyclohexylene oxide (Aldrich) 13.99 were placed in a pressurized reactor together with 90 g of isopropanol (molten t1.), and the ,
The reaction was carried out at 50° C. and 100 psi for about 1 hour. During this time, an exotherm to 63°C was observed. The final reaction conditions were set to 10
The reaction was carried out at 0° C. and 100 psi for 20-24 hours.

The product was placed in a rotary evaporator and the solvent (isopropanol) was removed under reduced pressure with heating. The analysis of the product (brown color) was carried out in the same manner as in Example 2.

Titration results Example 4: Total amine amount: 1070x 10'lol/g
2tertiary amine fl: 1075X 10-6mo
1157 Tertiary amine amount: 96x 10'mo
Approximately 9% of the total amine content in l/g had been converted to the tertiary amine form.

11'' CH3CH3CH3 H Similarly to Example 4, 172 g of (1) and 1,2-epoxy-3-phenogicypropane (from Aldrich) 22
9 and 95 g of 2-propanol were reacted together for 24 hours. The product had a light brown appearance. The amine content is
Measurements were made in the same manner as in Example 2.

-1-゛-Example 5 Total amine amount: 20th tertiary amine amount: Tertiary amine amount near 530X 10-6 mol/y 526x 10-6 mol/g 446x 10'mol/g CH2 It-CH2-CM -(CH2) 15CH3CH2 N(Cl12-CH-(CI+2) 15 CH3)
20th Similar to Example 4, 33 g of 659 (1), 1.2-1 poxyoctadecane (from Aldridge) and 100 g of isopropanol were reacted together. The final product was a yellowish "wax" that was solid at room temperature and became a viscous yellowish oil on heating (45-50°C).

The product was analyzed as in Example 2 with one modification. That is, since the product was found to be insoluble only in acetic anhydride and glacial acetic acid, it was necessary to use toluene as a co-solvent in addition to acetic anhydride and glacial acetic acid.

Titration results Example 6 Total amine amount: 754X 1O-6n+ol
/g tertiary amine amount: 673x 10'mol
/g Tertiary amine amount: 611X 10-6mo
Approximately 81% of the total amine content in l/g had been converted to the tertiary amine form.

Alkylation Example 7 of aminopolydimethylsiloxane copolymer where R is -(CH2)3-NH-(CH2)2NH2
and .

As in Example 1, 100 g of silicone liquid ①, 11.
6 g of ethylene oxide and 110 g of 2-propertool were reacted together. Reaction conditions were 50°C and 100psi.
It was 24 hours. The final product after solvent removal had a white milky appearance. There were two changes in the analysis of this product.

First, chloroborm was chosen as the solvent for measuring the total amine content and the tertiary amine content, since the product is insoluble in a solution of ether and isopropanol. The second is that 0.2N hydrochloric acid was used as a titrant. When this product was titrated for total amine content and tertiary amine content, the same reduction as in Example 6 was observed, with the titration solution becoming cloudy and a precipitate forming.

Titration showed that all the amines had been converted to tertiary amines.

Example 8 Anti-caries properties of aminosilicone shown by dissolution test of hydroxyapatite powder In these continuous exposure experiments, hydroxyapatite powder (3.5%) was first dissolved in a 5% silicone emulsion (60-70 d) for 10 minutes. ), filtered and washed with distilled water, then exposed to a 150-acetic acid solution at pH 5. Aliquots were taken at various time intervals and the hydroxyapatite powder was
Separated. Official Method
s of Analysis, As5ociatio
nof 0Hycial Analytical Ch
emists, edited by Sidney Williams,
Arlington, Purge-17', 632 pages.

The amount of phosphate ions in the aliquots was determined spectrophotometrically at 710 nlll with a molybdate solution according to J.D. 1984). The results are shown in Table 1.

(2) The toxylated aminoalkyl silicone had the structure (4) shown in Example 2.

The purpose of the experiment was to determine whether amine silicones with tertiary amines are effective anti-caries agents.

The results are shown in Table 1.

Table 1 This experiment shows that after 60 minutes of exposure to the acid solution, the untreated powder loses 438 ppm of phosphate ions, while that treated with the modified amine silicone of the present invention loses only 3 (i5 ppm of phosphate ions). It is obvious that it will be lost.

The kneaded toothpaste of the present invention was prepared by adding each component to Hover 1 to mixer and mixing until the mixture became a uniform paste. %).

Example 9 Natroso 1 glycerin water alumina T　l　O,.

50M Chlorhexidinyl]su-1~ Fl avor 771711.25
% 27% 10% 50% 05% 4.25% 1% Propoxylated 4% Aminoalkyl silicone (compound (1) reacted with propylene oxide) Example 3
Reference) Lauramine oxide 1% Cocamine oxide 1% Natro￥i' 2
50M is 1Iercules, Wilmingto
n.

It is a commercially available hydroxyethyl cellulose (nonionic water soluble polymer) gum from DelaWare. Alumina 3
No. 31 is a M2O3 trihydrate abrasive available from Aluchem. Navor 77171 is International
1ona INavors and Fragran
Available from ce company. Lauramine oxide and cocamine oxide are manufactured by Ar1ak Inc. Inclustrial Chemic/Is Div.
It is a surfactant made by Ision.

Example 1O Natrosol 1.25% Glycerin 27% Water

10% alumina 331
50%T i 020.5% Chlorhexidine gluconate 4.25%Fl
avor 77171 1%■
Toxylation, % Aminoalkyl silicone (Compound (1) reacted with ethylene oxide, see Example 2) Lauramine oxide" Camine oxide 1% 1% Husband 1" 1u Glycerin water Kel colo id Polyol ■ Alumina 331 Gluconic acid Kurylhexidine Flavor 77171 7% 15% 1% 16% 49% 4% 1% Propoxylation 2% Aminoalkyl silicone (compound (1) reacted with propylene glycol) Ar
ocel-801% Tween-801% and elcoroid-3 are from Kelco, C1ar
Nisdergum Propylene Glycol Alginate, available from K. K., New Jersey. Polyol ■ is a mixture of sorbitol and hydrogenated corn syrup available from ROQuette. AraCel
-80 and Tween 80 are surfactants available from ICI America, Inc. and are sorbitan oleate and polysorbate-80, respectively.

Example 12 Glycerin 7% water
1
5 %1 (elcolloid-81% polyol ■ 16% alumina 331 49% chlorhexidine gluconate 4% Flavor 7
7171 1% aminoalkyl silicone (compound (1) reacted with ethylene oxide, see Example 2) Δr/Pcel -801% Tween-80 4% elcaloid-S Ruhexidine Flavor 77171 7% 2% 14% 42.6% 4% 1% Aminoalkyl silicone (compound (1) reacted with propylene glycol) Ar
ocel -801% Tergitol NP-150, 5% water
19.
9% Pluronic F-874% Pluronic F-87 to B 5F-Wyand
Polyoxypropylene/polyoxyethylene block copolymer surfactant available from Otte, Parsippany. Tergitol NP-1
5 is a polyoxyethylene (15) nonylphenyl ether surfactant available from Union Canbide.

Example 14 Glycerin 7% water
11
．． 3% polyol Ill 20
．． 6% alumina 331 47
．． 7%T 10. , 0
．． 5%1-1ercules WSPM 1
017 4 Nisidine to 1.3% Chlor Gluconate
4.1%Flavor 77171
1% aminoalkyl silicone (compound (1) reacted with propylene oxide) Twe
en-601, 1% tlercules WSPH1017 (test product) is lauryl cellulose ether gum. Ar1acel
-60 is a simple tanstearard surfactant available from ICI America. Tween-60 is polysorbate-60, also available from ICI America.

11 length glycerin 7.2% water
11
．． 3% polyol III 20
．． 6% alumina 331 47.
7%T i O20-5% 1-1ercules WSPM 1017 1.
3% Chlorhexidine Gluconate 4.1% Fl
avor 77171 1% ethoxylated 4.1% aminoargyl silicone (compound reacted with ethylene oxide (1) Tween 1.1% Example 16 Aldehyde chemical reactivity test of amine silicone Evaluation of aldehyde chemical reactivity of amine silicone In order to
Various amine silicone emulsions were mixed with 2-furaldehyde and stored overnight in the dark to develop color. 2-
Furaldehyde was distilled before use. The following mixtures were prepared: Solution No. Component 1 Chlorhexidine + furaldehyde tenglycine 2 Furaldehyde + aminoalkyl silicone 3 Furaldehyde + ethoxylated aminoalkyl silicone 4 Furaldehyde + propoxylated aminoalkyl silicone 5 Furaldehyde 4-DC- 929 Furaldehyde + pS343 Chlorhexidine - Aminoalkyl silicone Chlorhexidine + Ethoxylated aminoalkyl silicone Chlor 10 Furaldehyde 11 Chlorhexidine Propoxylated aminoalkyl silicone The aminoalkyl silicone used was the compound (1) of Example 2. (1) The toxylated compound was (1) 1-hexylated compound (1) (see Example 2). The propoxylated compound was propoxylated compound (1) (see Example 3). The aminoalkyl silicone and the modified aminoalkyl silicone were used as a nonionic emulsion with a solid content of 30%.

DC-929 is a cationic emulsion manufactured by Dow Corning. p3343 is a nonionic emulsion of polydimethylsiloxane (126,000>15% molecules).

These solutions were ranked according to the intensity of their color.

2>1>5>3.9.4. > Dark brown Brown 6, 10 > 8.11 > 7 Very bright Opaque Opaque bright yellow White Colorless primary amine-containing amodimethicones (#2 and #5) all developed strong color, but those containing tertiary amines (#3 and #
4) has a yellow color, and its intensity is lower than that of the control solution (
#10) PS343 had no amine functionality and produced color development comparable to the control.

These results clearly demonstrate that the amino silicone of the present invention has inherently low chemical reactivity with strong staining aldehyde reagents.

Example 17 Clarifying agent The prophetic information is as follows: Ingredient formulations are as follows: Concentration % Modified amodimethicone (prepared in Example 2) Lauramin No. 4. Cyto (Armak Ar0IIIOX DHHC-Shi) Water 96% Glycerin (US Pharmacopoeia) Ethanol Flavor D & CYellow #10 FD & CBlue #1 20% Chlorhexidine Gluconate (LOnZa 5pectrodync) 1.00 0.30 45.84915 50.00 2.00 0.25 0.00060 0.00025 0.60 To produce a deodorant, 0.2% lauramine oxide is dissolved in water, and then amodimethicone is added and emulsified. The emulsion thus prepared is added to glycerin and mixed. Add 9 parts of ethanol and 1 part of ethanol, mix, and then add to the mixture. Add dye and mix. Finally, chlorhexidine is added and mixed to obtain a rinsing agent.

Example 18 The preliminary formulation for the transparent anti-warming agent is as follows: Ingredients 70% Sorbitol Solution Water Modified Amodimethine (Prepared in Example 3) Tercxitol N1) 15 Water Ethanol (200P F ) Concentration % 50,00 43,69915 1,Oo 0,39 2,06 2,00 Fragrance
0.25D&C Yellow #10
0.0006OFD&C Blue
e #1 0.00025
20% gluconic acid chewing hexidine 0.60 (
(manufactured by Lonza 5 pectrodyne) A desiccant agent is prepared as follows: Mix sorbitol and water. Amodimethicone 0.0
Emulsify with 9% Tergitol and water and add to the sorbitol/water mixture. Dissolve 0.30% Tergitol in ethanol and add fragrance. After mixing, the fragrance mixture is added to the silicone emulsion. Add dye and mix.

Finally, chlorhexidine is added and the preparation is mixed to obtain a clear rutting agent.

It is to be understood that the individual embodiments of the invention illustrated and described herein are for representative purposes only. Variations in the illustrative examples that do not depart from the express teachings of this disclosure are intended to include, but are not limited to, the teachings herein.

Unilever Namrovi

Claims (7)

[Claims] (1) Formula A in an orally acceptable vehicle: ▲Mathematical formula, chemical formula, table, etc.▼A (wherein a is 0 to 2, n is 1 to 5, and R is a monovalent is a group, R^1 is a divalent hydrocarbon group, R^2 is -CH_2-CH(OH)-R^3, and R
^3 is selected from the group consisting of hydrogen and a monovalent hydrocarbon group, b is 0 or 1, and m is 1 or 2. (2) Furthermore, the formula B R^5aR^4cSiO_(_4_-_a_-_c_)
__/_2B (in the formula, R^4 and R^5 are the same or different monovalent groups, and a
and c is an integer of 0, 1, 2 or 3, a+c is 0,
The dentifrice according to claim 1, characterized in that it contains at least one unit having the following formula (1, 2, or 3). (3) The toothpaste according to claim 2, comprising a toothpaste containing a humectant and an abrasive. (4) The toothpaste according to claim 2, comprising a mouthwash containing ethanol. (5) Formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, x and y are randomly arranged, and x is 750~
1250 and y is 25 to 100). (6) Formula ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ The dentifrice according to claim 2, characterized in that it has the following. (7) Formula C ▲There are mathematical formulas, chemical formulas, tables, etc.▼C (In the formula, a = 0 to 2, m is 1 to 2, R is a monovalent group, and R^1 is 2 is a valent hydrocarbon group, R^2 is -CH_2-CH(OH)-R^3, and R
^3 is a monovalent hydrocarbon group or hydrogen) and the formula R^5aR^4cSiO_(_4_-_a_-_c_)
A dentifrice comprising an aminoalkyl silicone copolymer comprising at least one unit having _/_2.